CA1051030A - Alkanol amide compositions and process for their production - Google Patents

Abstract

ABSTRACT
A process for producing novel alkanol amide compositions of low melting point is disclosed. It involves reacting alkanol amines with esters whose acyl groups include some groups with a positioned alkyl group side chains containing two or more carbon atoms. The novel alkanol amide compositions produced in the process exhibit useful and valuable properties particularly when used in combination with various detergents in aqueous washing solutions as set forth herein.

Description

3~ ~
ck~roul~d o th~ Inventioll . _ Thi~ i.n~ention re.l.ates to the preparation o~ alkanol amide.s of fatty acids whose ~cyl groups have from about 8 to about 20 carhon atoms, to mixtures o~ such amides, and to uses of such mixtures.
The production of alkanol amides by a reaction with alkanol amines o~ esters derived from na-tural oils and fats in a base catalyæed process has been known for some time~
The process is described in U. S. Patents 2,464,094; 2,877,246;
3,107,258, 3,257,436 and 3,3951162 and in J. Am. Chem. Soc.
64, 2498 (1942). The process produces monoalkanol amides when using monoalkanol amines as reactant while it produces di-alkanol amides when using d~alkanol amines as reactant.
The monoalkanol amides are us~ful in detergent compositions as described in U, S~ Patents 2,383,~37 and 3,332, 878. The dialkanol amides also are use~ul in detergent composi-tions as described in U. S. Patents 2,607,740 and 2,870,091.
In many instances the dialkanol amides are preferred because of convenient, low, melting points which permit handling as liquids at ordinary temperatures of 25-75C. Unfortunately, this virtually has requ~red the use of natural source ester ~ate~ials because there has been no conveni.ent source of usable synthetic esters for the base catalyzed reaction with dial~anol ~-amines as that process is known rom the prior art, One of the preferred sources of low cost synthetic ~ource esters is ;
via the catalytic reaction of olefins with CO and alcohol as ~ -described for example in U. S. Patent 3,168,553. Unfortunately, the esters obtained this way do not react readily with dialkanol amines. An aspect o~ this invention is the discovery that this trouble is cause~ by the presence in such synthetic esters of a substantial percentage ~15-50 percent) of esters havin~ . .`
branched chain acyl groups, many of which acyl groups have cbf ~)5~ 3~ ~
~-ethyl, ~~p~opyl, ~-butyl. and higher alkyl group subsl-itukion located in the carbon chain posit.ion alpha (a) to the carbon ~ atom of the ~-C-) group.
o , To avoid this prob].em of poor reactivity o~ branched .`- :
esters it has been necessary in the past to use the prior art ~:~ acyl halide route wherein an acid having a desired acyl group .~ ~
such as dodecanoic or tridecanoic is converted to acyl halide, . : :
such as acyl chloride, ana then the acyl halide is reacted 10 with dialkanol amine. U. S. Patents 2,4111434 and 3,$03,891 ~ .
describe such processing. . ~. .
Summar~ of the In~ention ;: -:
:
In accordance with the invention, a new process is provided which produces novel alkanolamide compositions use-: ful in variaus ways such as foam boosters for washing composi-tions, as fabric treating agents, and the like.
A feature of the invention is the discovery that lower alkyl e~ters of aliphatic monocarbox~lic acids whose : ~ acyl groups contain from about 8 to about 20 carkon atoms and ;
.: . . . . . .
; 20~ are branched carrying in 'che ~ position ~of the acyl groups) an .
; alkyl substituent ~t least two carbon atoms in length are sub-stankially unreactive with di lower alkanol amine but do react with mono lower alkanol amine and that by applying a two step reaction sequence, alkanol amines having high purity and new, highly desirable, properties can be obt~ined readily and at low cost from ester mlxtuxes containing these esters.
The significance of this discovery is that it permits : ~
the production of valuable dialkanol amides having low melting ~` ;
points, by the ester-amine amidation reaction, using esters 30 produced synthetically and which contain some branched chain :
a~yl groups. The invention ~hus satisfies a long ~elt need :
of providing new amides at.low cost from synthetically produced ; .
.
ab,~ - 2 - ~
: -1()5~acyl ~roups. Not only are the new synthetic amides at least equivaler,t to the prior ar-t amides in most pex~ormance aspects, but they are actually superior to the prior art amides in selectable propertiesc Accordingly~ the present invention relates to a process for producing a1kanol mixtures in which a di lower alkanol amine is reacted with a mixture of lower alkyl esters .
of aliphatic monocarboxylic acids whose acyl groups contain from about 8 to about 20 carbon atoms. The mixture of esters : ~
10 reacted is ch~racterized in that rom about 2 to about 20 mol ~ .
percent of said ester mixture is branched ester in which the acyl groups carry in the a positlon an alkyl substituent at least two carbon atoms in leng~h. The esters which are of this branched structure are substantially unreactive with the . dialkanol amine and therefore are not converted to amide although other esters co-present may xeact with the dialkanol amine to produce dialkanol amides. The amount of dialkanol amine employed in this reaction is sufficient to convert at least 10 mol percent of the ester mixture into dialkanol .
:20- amide. The product from the preceding reaction wh~ch contains dialkanol amide plus unreacted ester is subse~uently reacted . with mono lower alkanQl amine to conYert unreacted ester into mono lower alkanol amide thus producing a mixtuxe o dialkanol amide and monoalkanol amlde. Xn th~s second reaction, the esters that did not react in the first reaction, including the branched ester, react readily to produce virtually complete QVerall conversion o~ feed esters to amide without a need for :
.: large excess of either unreacted amine or unreacted ester to xemain in the amide product unless such is des;red-and brought 30 about by the use of excess of one reactant or the use o condi tions which bring about only partial reaction. Preferably bot~
` ~aid xeactions are carried out i~ the presence o~ a base c~/ - 3 - .

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c~t~lyst.
I t has been discovered tha~ alkanol amides p~oduced by the fore~oing process have excellent properti~s in detergent compositions, The amides are a mixture of mono lower alkanol amides and di lower alkanol amides in which the acyl groups contain from about 8 to about 20 carbon atoms. At least 10 ' mol percent of the mixture is di lower alkanol amide. From "
about 2 to about 20 mol percent of the amide mixture is mono lowex alkanol amide whose acyl groups carry in the a position an alkyl substituent at least two carbon atoms in length.
-` ' According to another aspect o'f the invent~on, a washing composition'is provided consisting essentially of a mixture of mono and'di lower alkanol amides in which the ,~
~,~ acyl groups are open chain acyl groups containing from about ;
8 to about 20 carbon atoms, said mixture being characterized ,' ', in that at least 10 mol percent thereof is di lower alkanol ' amide and further in that from about 2 to about 20 mol percent ,~
'1 of said mixture is mono lower alkanol amide whose acyl groups ', carry in the ~ position an alkyl substituent at least two ,, 20 carbon atoms in length; and ~2) an organic detergent surfactant ~,~ selected from the group consisting of anionic detergents, cati~onic detergents, nonionic detergents, ampholytic detergents, , ' zwitterionic detergents, and mixtures thereof suitable for ' ;
', ' use in water. The amount of amide in the washing composition ~ 'xanges from ~bout 0.05 to about 25 percent b~ weight. This . .
w~shing composition is preferably use~ to form with water an ~ueous washing system. The amount of amide used in such a system ranges from about 0.05 to about 25 percent by weigh~
' of the 'total of amide and organic'detergent surfactant. The 30 , total of ami.de and organic detergent surfactant in s~ch a system is from abou~ 0.05 to about 1.0 weight percent of the , system.

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In acldjtion ~o the forego.iny, ~he present invention relates to an improven)ent in a met~lod for washing articles in an aqueous soluti.on of al~nol amide composition and organic detergen~ surfactan~ using thP foreyoing w~shing composition.
Descri~tion of the Invention ~ ~:
Alkanol. amides, also called hydroxy alkyl amides, have valuable detergent properties. They are used with various detergents to enhance foaming, par~icularly in a~u~ous solutions, to enhance (increase) the viscosity of washing solutions, to form synergistic cleaning mixtures, and in other ways well known to those skilled in the art. In many instances, aI~anol ~: :
amides having low melting points are particularly desired to `
facilitate the handling thereof as liquids at moderats tempera~
tures such as 25-75C, By virtue of the present invention, a new amidation process is provided which can utilize the base catalyzecl re-act~on of alkanol amines with esters having a significant per- ;~
centage of br~anched chain acyl groups. The present process for producing alkanol amides pxeferably utilizes a mixture of ;~
, . . . .
0 esters containing:some esters whose acyl groups (acid radicals) re of branched chain carbon skeletal struc~ure having a ;~
.. . ~ , : positioned alkyl groups or branches containin~ two or more : carbon atoms each such as ~,ethyl, a-propyl, and a-butyl, and ~ .
higher alkyl. In the first stage of the present process, ~;?
the esters are reacted with di lower alkanol amine. Lower : alky} esters of aliphatic monocarboxylic acids whose acyl .
~.
groups have from about 8 to about 20 carbon atoms and wherein the a carbon atom of the acyl groups is free of a positioned .
alkyl branches ha~ing more than onecar.bon atom react readily ~ 30 with di lower alkanol amines to produce di lower alkanol '. amides leaving virtually unreacted co-present 0sters whose ;.:
acyl groups carry ethyl, .propyl, bu~yl, or higher alkyl ,~
.~

cb~

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branches on the a c~rbon ~-~om o tlle longest carhon chain.
~'ref0rably the amount o~ di lower alkanol aminc fed at the ~irst stacJe of the process ls no~ in excess of that required to react with the portion of the feed esters whose ac~l groups are free of ~ positi.oned alkyl branches having two or more ~-carbcnatoms. Thus the presence of excess dialkanol amine in the product amide is avoided or minimized.
The first stage, or intermediate, product is a mix-ture containing ~1) di lower alkanol amides whose acyl groups are free o~ a positioned alkyl branches having more than one carbon atom plus (2) unreacted ester including ester whose acyl groups carry an ethyl, butyl or higher order alkyl branch at the a carbon atom. The intermedlate product is then reacted with mono lower alkanol amine in a second stage. The unreacted ester in the intermediate product reacts readily in the second stage to produce mono lower alkanol amide. Preferably the amount of mono lower alkanol amine fed at the second stage is ;~
not in excess of that required to react with the unreacted `~
ester in the intermediate product.
The present process may be performed in a batch, semi-cont~nuous or continuous manner. The order of addition of the reactants in each step is not particularly critical;
however, the sequence of reaction of ester with di lower alkanol amine and then with mono lower alkanol amine is important;
For ease of control, it is preferred that in the first stage the di lower alkanol amine is added intermittently or continuous- ;
ly to the ester-containing xeaction mixture and that ln the second stage the mono lower alkanol amine is added intermittently or continuously to the amide-containing reaction mixture from the first stage. ~
To 3implify overall operations and reduce handling and other processing expenses, the present two-step processing ..
. ' ` ' ' .
cb; - ~ ~
,.

,, . , . - . . ... . ~ . ._ . .. . . .. .. ~ . . . . . ...... .... .

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s~quence is pr~ferably applied in a sln~le operatincJ sequence to starting ~ster mixtures which h~e thc desired distribution in regard to molecular weight (or numher of carbon atoms per acyl group) and in reyard to various lenyths of a positioned alkyl branches thereby produciny directly the desired amide product without requiring subsequent analyses and blending of -amiaes. Ester mixtures used in the present process may be obtained by blending various suitable synthetic or natural source esters in appropriate proportions~
Following the amidation reactions it is usually desirable first to allow the product to stand for a period of time of from about 1 minute to about 48 hours at a tempera-: . . .
ture of from about 25 to about l50~C to permit redistribution ~stabilization) to take place.
Following the redistributi~n, where such is used or subsequent to the second stage where there is no redistribution step, it is usually desirable to inactivate the catalyst remain-~, ing in the second staye reaction product by neutralization `, thereof with a suitable organic or inorganic acid. Suitable ', ~ 20 acids include H2SO4, HCl, acetic acid, and the like. Normally ? the neu~ralization products are alIowed to remain in the pro-.1 - , ' , .
duct amide since the a~ount thereof is quite small on a weight ~I basis. ~ `

;~ ~ In particularly prefexred esters used in the present process, from about 5 to about 10 mol percent of said mixture , is branched ester in which the acyl groups carry in the a posltion an alkyl substituent at least two carbon atoms in length.
Numerical values for the moI xatio of dialkanol amine to lower alkyl esters employed in the first reaction or the pxesent process vary somewhat depending upon the starting esters and the product amide desired but in general they range cbj' : ' ' ' .':

~)5~3~
from about 0.25:1 to about l.S~ preferrecl uppex llmi~
on the mol ratio of dialkanol amine to ester fed i5 about 1.2:1. ~ ;
Where particularly outstancli.ng product amides are desired for detergent compositions; the ratio of dialkanol amine to ester ~ed at the first reaction is preferably in the range of about 0.4:1 to about 1:1. For more highly preferred detergent com-positions using the preferred ester feed obtained by the re-action of olefins with CO and methanol, the ratio of dialkanol ;~
amine to ester is from about 0.5:1 to about 0.9 In a specific embodiment, the amount of dialkanol amine fed at the first stage is that which produces a product ~ amide mixture which is about 50 mol percent dialkanol amide.
s Product amides have excellent viscosity and washing properties. ;
In anothex specific embodiment, the amount of di-I alkanol amine fed at the first stage is that which produces , . . . .
a product amide mixture which is about 70 mol percent dialkanol amide. Product amides have excellent viscosity and washing properties and in addition have convenient melting points ~' for many uses.
.j , , ~. .
In another specific embodiment, the amount of di-' ~ alkanol amine fed at the first stage ~s that which-produces a product amide mlxture which is about 90 mol percent dialkanol . ( . . .
amide. Product amide is outstanding in terms of melting points and viscosity properties. `~
., .
Where maximum dialkanol amide content and low melt- ~
ing point are desired, the amount of dialkanol amine supplied ~ ;
at the first stage of the process is about 100 percent of the j stoichiometric amount required for reaction of all of the feed esters whose acyl groups carry no ~ positioned branch with 30 two or more carbon atoms Preferably this is the maximum amount of dialkanol amine used where high purity-of product ; is deslred.
: ' :
cb~ ~ 8 - `

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The ~m~un~' of mono low~x ~ anol amin~ f~d at the second s~age is L)re~rably not substantially in excess of the amount required to react with all unreacted ester remaining at that point in the interrn~diato product from th~, first stag~.
~lthough one may ~eed even large amounts o~ excess amine as far as the process itself is concerned, usually it is preferred to minimize purification and recovery problems o~ product ~ , amides and thereby simplify the overall process by holding the amoun~ of excess mono lower alkanol amine fed below 20 percenk, preferably below about 5 percent. The mol ratio of '~ monoalkanol amine to unreacted ester in the second reactlon ~, preferably is in the order of from about 0.9:1 to about 1.2:1, especially about 1:1. This holds to a low value the amount '''' -,, ~
'~ of excess'amine in the product on the one hand and on the '' other hand holds to a low value the amount of excess ester , in the product.
' ' To provide preferred ratios in the overall process, ,~
including a high content of dlalkanol amide suitable for most~
feed esters containing 10 percent or less of said branched 20 ester, the mol ratlo of dialkanol amine to lo~er alkyl estexs ~j .
~ employed in the first reaction falls in the range of about .
, ~ 0.5:1 to about 0.9:1 and the mol ratio of,monoalkanol amine ' to said unreacted ester in the s,econd reaction 1s in the order '', , o~ about 1:1. , ' ' , ~ ' In elaboration o~ the foregoing, it is evident that .
acyl groups which are free o~ a positioned alkyl branches having ~ '~
I more than one carbon atom include acyl groups whose a carbon atoms carxy two'hydrogen atoms, those whose a caxbon atoms carxy two methyl groups and those whose ~ carbon atoms carry a hydro- ' 30 gen atom and a methyl group. The leng~h of the u positioned -~
alkyl branches which contain two or more carbon atoms each rangesupward from ethyl to include alkyl gxoups with awhole ~b/

. . , ~

~ 5~ 3~ ~:
number of carbon atoms which does not exc~d n-2 whexein n ls the total numbers o~ carhon atoms in the acyl g~oup. Prefer-ably the esters or amides with ~ positioned alkyl branches which contain two carbon atoms are most numerous, there being ~ -~
progressively smaller amounts of esters or amides containing the longer branches. Thus the esters with eth~l branches out-number the esters with propyl branches which in turn ouknumber the esters with butyl branches, and so forth.
,., Preferred esters used in the present invention usually contain not only branched esters whose acyl groups carry in the ~ posi~ion an alkylsubstituent at least two carbon atoms ! in length but also contain some a branched esters wherein the only a substituency is methyl. Such ~-methyl branched esters ;
react reaaily with the dialkanol amine of the present process ;l and when in admixture with a-ethyi, a~propyl, etc. bxanched ;j esters react prèferentially relative thereto with the dialkanol ~i amine in the first reaction of the process leaving substantially : .
,3 all of the a-ethyl, a-propyl, etc. branchèd esters unreacted . and in the intermediate product fed to the second stage to ~ ;~
,j .. . .
;, ~; 20 Xeact with monoalkanol amlne in the second reaction. ~;

~ Generally speaking, ester for the first reaction is :i, . .
preferred~wherein from about 10 to about 65 mol percent of the ester mixture used in the first reaction is brana~ed ester in which the acyl groups aarry a methyl graup in the a position.
1 Such ~ester mixtures are desired for their low cost, for their ', excelIent reactivity in the present process and for the valuable properties of the products produced thererom when using the present process. Especially prefexred ester mlxtures in regard .~ . ~ . . . ~ .
-~ to this aspect are those wherein from about 12 to about 25 mol , 30 peraent of the mixture is branchèd ester in which the acyl ~ ;

~groups carry a methyl group in the a position.

The a caxbon atoms of the acyl groups of particularly , .
. ~:
c~ 1 0 - `

3~
preferrcd es~ers carry at lea~ one hydroyen a~om. Preferred esters used in the pres~n~ invention usually contain not only the ~oregoing branched esters which carry methyl, ethyl, pxopyl, .' etc. alkyl groups on the ~ carbon atoms of the acyl groups but , in additlon contain some esters which carry two hydrogen atoms ~ , ; on the a carbon atoms of the acyl groups.
~' The preferred esters which carry on the a carbon '' atoms of their acyl groups two hydrogen atoms or which carry ' ~ on the ~ carbon atoms of their acyl groups one h~drogen atom ~ ~: . 10 and one methyl group react readily with di lower alkanol amine at the irst stage reaction and produce excellent'dialkanol ,- amides provided the esters remaining can be' conve.rted to mono-,, .
alkanol amides as in the present process. Without such sub- ' sequent conversion, however, the amides at th,is point usually are too impure to compete successfully with natural source dialkanol amides. In addition, if an inadequate amount of di lower alkanol amine is ava~lable at the first stage so that some of these hydrogen-hydrogen or hydrogen-methyl estexs cannot react at the first stage, these esters xeact readily .
~lth the mono lower alkanol amine in the second stage reaction. ' ,. , .~ Thus, at the second stage reaction, preferred esters o, the , mtermediate product fed thereto can include (1). esters whose ac~l groups carry'two hydrogen atoms at the a carbon atoms, ,i ~2) esters whose acyl groups,carry at the ~ carbon atom one h~drogen atom and one methyl group, and C3). esters whose acyl ~roups carry at the ~ caxbon atom one hydrogen atom and one : ' , ', alk~l group having two or more carbon atoms.
I The product obtained from such ester mixtures in .
'~ the present two-s~age processing when using in the fixst stage ,~ less than a stoichiometric amount of di lower alkanol amine for all the esters thexefore may con~ain the first thr,ee components o~ the following list and'may contain the fourth and even some , ^ ~b/ - }1 - , ; ' .

~5~3~ ~:

; fifth component~ dependiny upon proportions:
- l - Dialkar1ol amide~ carrying ~wo hydrog~n atoms on the ~ carbon atom of the acyl groups

2 - Dialkanol amides carryiny a methyl branch on the u carbon atom of the acyl groups

3 - Mo~oalkanol amides carrying an ethyl, propyl, butyl or higher alkyl branch on the a carbon - -~
. . .
atom of the acyl groups .

4 - Monoalkanol amides carrying a methyl branch on the a carbon atom of the acyl groups ; 5 - Monoalkanol amides having two hydxogen atoms on the a car~on atom of the acyl groups The esters used in the present process are lower alkyl esters of carboxylic acids as set forth hereinbe~ore ~nd o~ lower a1kanols. It is evident that such esters are , generally referred to as alkyl esters corresponding to the ~ hydrocarbon group of the alco~ol component thereof; for exam-; ~ ple, methyl esters are based on methyl alcohol. It Will be ~`~
recognîzed that this term is distinct rom the terms a-methyl, 2Q~;a~et~yl, 2-methyl, 2-ethyl, etc. used to characterize the lengkh and location of branches ~n the acyl groups o~ the ` esters, Preferxed esters reacted are methyl esters. Such esters have excellen~ reactivity, are easily made, and in the amidation reaction liberate alcohol which~is xeadily recycled.
In addition to methyl esters, other alkyl esters of C8-C~O ~`
monocarboxylic acids can be used such as esters of ethyl, pr`opyl, and butyl alcohol but for commercial and other reasons they~are less preferred than the esters of methyl alcohol. ~;~
,. . . :
3Q~ In general, the acyl~segment of the esters used in tha present process may be selected from a laxge group. The esters may be derived from straight chain and branched chain~

~cb/ ~ 12 ~ 0 S ~ 30 sa~urat~d and unsatura~ec1, alip~la~ic monocarboxylic acids includinq caprylic aci.d, capric acicl, s~earic acid, lauric acid, myr.istic aci.~, palmitic acid, oleic acid, linoleic acid, linolenic acid, undecanoic acid, 2-methyl decanoic acid, 2~
ethy] n~nanoic acid, tridecanoic acid~ 2~methyl dodecal1oic acid, ;:
2-ethyl undecanoic acid, pentadecanoic acid, 2-methyl tetra-decanoic acid, 2-ethyl tridecanoic acid, 3-ethyl undecanoic acid, 4-propyl decanoic acid, and the like. Suitable esters . may be ~erived from mixed higher fatty acids or esters derived lO from animal or vegetable sources, for example, lard, coconutoil, rapeseed oil, 6esame oil, palm kernel oil, palm ~il, oliYe oil, corn oil, cottonseed oil, sardine oil, tallow, soya bean oil, peanut oil, castor oil, seal oils, whale oil, shark oil, and other fish oils; from partially or completely hydrogenated .animal and vegetable oils such as.those mentioned; from fatty and similar acias or esters derived from various waxes such as .:
beeswax, spermaceti, montan wax, coccerin, and carnauba wax.
In addition, suitable esters may be obtained from higher mole-cular weight carboxylic acids derived by ~xidation or other chemical processing methods from various starting materials .
f' ~ncluding paraffin wax, petroleum and similar hydrocarbons.
. Particularly preferred esters for the present process ~ ~:
are produced by a carbonylation reaction of olefinic hydrocarbons .;
having from about 7 to about 19 carbon atoms per molecule, with CO and with a hydroxyl compound such as methyl alcohol :~
¦ using various catalysts such as nickel, cobalt, iridium, -~ rhodium, palladium,.sulfuric acid, orcarbonyls such as cobalt carbonyl, etc. This process produces directly mixtures of esters having branched and unbranched carbon chain acyl groups. ;
3~ This process is described, for example, in U. S. Patent 3,168, ~553. Alternately~ branched acids or salts can be produced by other processes and later esterified with a lower alkanol ~ch ', , , ~ , :

. ~ cb/ ~ 13 -: .

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as methanol or ethanol. Branclled acids can he produced in several ways sucll as shown by U. S. Patents 2,607,787;
2,831,877; 2,~76,241; 3,205,2~; 3,296~286; 3,530,1S5; 3,~61, 951; 3,661,957; 3,678,083; and 3,718,676. Branched esters are also produced via esteri~.ication of acids obtained via oxidation of isoaldehydes, via ozonolysis of olefins, vi~
caustic fusion of synthetic or natural source alcohols, and in other processing as described in U. S. Patents 2,010,358;
2,042,220, 2,607,787 and 2,8~3,426. Thus directly or indirectly -~
via other processing such as esterification and blendiny one obtains methyl., ethyl or other al~yI esters having from about ~
8 to about ~0 carbon atoms per acyl group and containing from ~:
about 10 to about 50 percent branched chaln acyl groups, a ~ ~.
proportion of which of from about 2 to about 20 mol percent of the total acyl groups, has ethyl, propyl, butyl or higher alkyl branches carried by the a carbon atoms o the acyl groups.
Preferred esters used in the present process are esters of aliphatic monocarboxylic acids whose acyl groups have from about 11 to about 15 carbon atoms~ Such esters are ' ; ~ 20 characterized by excelle~t reactîyity in the process and by particularly use~ul propert~es o~ the product amides. Parti-. : cularly pre~erred are ester mixtures wherein some acyl groups have 11 carbon atoms, some acyl groups have 13 carbon atoms :, ~ , .
~nd some acyl group~ have 15 car~on atoms. In add~tion to I e~cellent reac~ivity, such ester mixtures have the advantage `~ thqt they are readily produaed at low cost. Outstanding ~
esters useful in the presen process are esters in which the ~.
acyl groups have 13 carbon atoms. Although pure C13 methyl ester mixtures are likely to be more expensive than the Cll, - 30 C13 and C15 mixtures aforesaid, the C13 amide products obtained :~
via the present process have outstanding properties in regard `
to viscosi~y in aqueous solutions. Ester mixtures~rich in ~ :~

c~ - 14 :105~3(~
~ters with C13 acyl groups (from al~out 40 to about 50 mol percent) are espc~ially desi.red for all ar~und excellellt re-activity, low cost and reacly availability ~nd for excellence of amide product.
Pref~rr~d olefins xeacted with C0 and methanol or C0 and water to provide starting materials for the present process have from about 10 to about 14 carbon atoms per mole cule, including decene-l, undecene-1, dodecene-l, tridecene-l, tetradecene-l, dodecene-2, 2-ethyl decene-1, 2-propyl nonene-1, ~:
3-ethyl decene~l, and the like. Preferred olefins of the about 7 to about 19 carbon atoms pex molecule range~ as well as of the about lO to about 14 carbon atoms per molecule range have even numbers of carbon atoms per molecule; howe~er, other olefins such a~ olefins h~ving 7, 9, 11, 13, lS, 17 ~nd 19 carbon atoms can be used to produce materials with acyl groups having even numbers of carbon atoms. Frequently it is convenient .
tQ select olefins for this process to.~provide directly, without need for separate production, analysis, or blending of esters `~
or of amide, the desired distrlbution of car~on atoms in the .. . ;: ,.
acyl groups of the amide product as set forth hereill. Preferr~
, ed olefins reacted to produce esters or acids are predominantly '~ .: terminal olefins and preferably of predominantly straight chain carbon skeleton ~unbranched~. and substantiall~ free of remote branahes carried at the ~, ~, or r carbon atoms or ~urther removed ~rom the (.-C~) group. Branched skeleton olefins may :' o ' ~ , be used and may give rise to branahed esters whose acyl groups contain side chaln alkyl groups. Although pure esters are ;
preferred, the present proces~ does not requir~ the removal 3D of all residual unxeacted olefins in admixture with the staxt-lng esters since such olefins can be separated from the amides and recycled. : ' . ~ .
, cb~ 15 ~ . .

.~ , .

~)5~030 In gener~l, the ~lkanol ~mines use~ul include symmet-rical, unsymmetric~l, normal and iso derivatives, such as mono-ethanol amine, diethanol amine, ~onoisopropanol 3mine, diiso-propanol amine, monopropanol amine, dipropanol amin~, mono-butanol amine, dibutanol amine, monopentanol amine, dipentanol :.
amine, monohexanol amine, dihexanol amine, monoethyl monoethanol amine, methoxypropan-ol-3; 2-N-methylamino-propandiol-1,3; : :
monoethanol monopropanol amine, monoethanol monobutanol amine;
alkylol polyamines such as alkylol derivatives of ethylene -~
diamine~ diethylene triamine, and ~riethylene tetra-amine as, for example, hydroxy ethyl ethylene diamine, diglycerol mono-amine, diglycerol-di-amine, hydroxy-alkyI amines derived from other polyhydric alcohols, ~ncluding glycols, sugars and sugar alcohols such as ethylene glycol, diethylene glycol, glycerol, dextrose, sucrose, sorbitol, mannitol and dulcitol.
The amines used in the reaction are preferably lower ., aIkanol amines having from 2 to about 4 carbon atoms per alkanol group. These amines~are preferred because of theix excellent reactivity and because of the properties of product amides .-. ; 20 obtained when such amines are used. ~articularly preferxed -amines used in t~e first and second reactions are diethanol amjine and monoethanol am~ne, respectively. Other prefèrred amines are.diisopropanol amine and mono1sopropanol amine, ' xespectively.
i The physical conditions used in the reactions are ` . ~
not particularly critical and in general are similar to those known in the prior art for individual reactions of natural `J source esters with dialkanol amine.or with monoalkanol amine. .
. ~ Condit1ons for the first reaction are similar to those used for ' 30 the prior axt reaction of diethanol amine with natural source esters such as methyl esters ob~ained from coconut oil by trans-, t, et~terification wherein the product is dialkanol amide.
;j" :

~: cb~ - 16 -:: : , :

1(~5~)3~
Condi~ions for ~he second r~action ar~ similar to those used for th~ prior art reaction o~ monoc~h~snol amin~ with the natural source 2is~ers.
Thus temp~ratures in the range of about 25C to about 150C are pre~erred for each of said reactions. Especially preferred temperatures are in the range of about 40C to a~out 75C for the first reaction and in the range of about 75C to about 125C for the second reaction. Since the second reaction is usually somewhat slower tnan the first reaction, 10 it is usually preferred to employ a hi~her temperature in the ` second reaction than in the first reaction. Typical temperature~
are abou~ 60C and ahou~ 105C for the first and second stages, respectively. Pressures depend to some ex~ent upon temperature -~
and range from about 5 mm o~ mercury absolute to about 25 atmospheres with absolute pressures of from about 10 mm to about 760 mm preferred. Typical pressures are a~out 30 mm of mercury absolute, about 100 mm of mercury absolute and about ` atmospheric pressure.
s Catalysts ~re fre~uentl~ employed to advantage in ;, 20 the reactions particularly in the second stage reaction. Cata-/~ lysts may be dispensed with in the ~irst reaction particularly when the higher temperatures of 100-150C are used; however, since it is usually desired to have a catalyst at the second ; reaction, it is preferred ~o add an ef~ective amount o~ the catalyst at the first reaction and conduct the fi.rst reaction under the lower temperatures indicated for catalyzed reaction carrying the ca~alyst through to the second step reaction.
Any sultable catalyst may be used in the present proces Known catalysts include salts, such as the hydro-30 chloride of the amine used, and base catalysts, such as an alkall metal, an alkali metal alkoxide, amide or other alkali metal compound which will generate an alkali metal alkoxide . : .
' ' cb~ - I7 -' - . :

l~S~30 on contac~ Wit]l an alcohol. E~referx~d catal~sts ~re alkali metals, alkali metal alkoxides, and alkali metal amides. Of these, the alkali metal alkoxides, ~specially those containiny ~r~m 1 to 5 carbon ~toms, are particularly preferred because of their excellent catalyt;c activity and ease o~ use and ease o~ subsequent inactivation via neutralization with an acid.
The alkali metal alkoxides include the sodium, potassium and lithium alkoxides derived from monohydric alcohols ~uch as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, and pentanol Especially satiæfactor~ and preferred is sodium methoxide.
; In place of or in conjunction with the alkaIi metal alkoxides, other catalysts which can bq utilized are the alkali metal amides! such as sod~um amide, potassium am~de and lithium ;:! amide; and the alkali metal aminoalkoxides cont~ining from 1 to S carbon atoms, the latter being derived, by way of example, l b~ the interaction of an alkali metal such as sodium, potassi~
; or lithium with an hydroxy amine such as monoethanol amine, diethanol amine, monoisopropanol amine, or other hydroxy . I .
amines, or by dehydration of an alkali metal h~dxoxide solution ~n the h~droxy amine.
The amount of catalyst used is an effective catalytic amount w~ich in general ranges upward from about 0.1 mol per~
cent to about 20 mol percent based on the ester ~ed. ~lthough greater amounts can be used, such is usually unnecessary and creates problems of removal or recovery and expense. Prefer-ably the amount of catalyst is from about 1 to about 10 percent ~nol basis). Typically, the amount of catalyst is about 9 per cent. The amidation reaction may be carried out without a .. . .
~ 30 solvent or with the aid of a solvent such as methanol, which , i . .
is a partic~arly powerful solven~ for the lowex alkyl amines.
-- In some instances, it i~ convenien~ to supply alkali metal ab/ ~ - 18 -, .

~ OS~0~3~
alkoxide as a solution in alcohol solvent r~t.linin~ the solvent.
In addition, alcohol liberated in the reaction, if not removed, ~ay be retain~d in the reaction system.
Re~ction time is important but not critical. In general, the preferred time or each stage is at least the time necessary to reach the conversion desired for that stage.
Longer times are permissible but in general one does not use a longer time than necessary so as to avoid delay in processing and to minimize side reactions. Times of from about 30 seconds to about 5 hours for each of the stages are suitable with a time of from about 2 to about 60 minutes preferred for the first stage and from about S to 120 minutes preferred for the second stage. Typical reaction times are 20 minutes and 40 minutes for the first and second stages, respectively.
In a preferxed com~ination of certain o~ the fore~
going preferred aspects of the present invention, diethanol amine is reacted at a temperature o from about 40C to about 75C with a mixture of methyl esters of aliphatic monocarboxylic ~cids whose acyl groups contain from about 8 to about 20 carbon ~, 20 atoms, said mixture being characterized in that from about 2 to about 20 mol percent of said ester mixture is branched ester : in which the acyl groups carry in the a position an alkyl sub-stituent at least two carbon atoms in length, said esters being 9ubstantially unreactive with diethanol amine. The amount of diethanol a~ine employed in this reaction is sufficient to con-yert at least 10 mol percent of the ester mixture into diethanol amides, The product from the preceding reaction is reacted in ~l a second stage with monoethanol amine at a temperature of from 7''. about 75QC to about 125C to convert unreacted ester into mono-ethanol amide. Both said reactions are carried out in the . s~
presence o sodium methoxide catalyst.
In a pre~erred embodlmen~ of the feature~ o~ the cb/ - 19 -CI 3~ ~
present invention a procecs is proYicled for ~roducin~ alkanol amides in ~hich a di lower alkanol amine is reacted with a mixture of methyl esters of alipllatic monocarboxylic acids whose acyl yroups contain from about 8 to ~bout 20 carbon atoms, said mixture being characterized in th~t Xrom about 2 to about 20 mol percent o~ said ester mixture is branched ester in which the acyl groups carry in the ~ position an alkyl sub-stituent at least two carbon atoms in length, said branched ester being substantiall~ unreactive with said amine. The amount of amine employed is suf~icient to convert ~ least 40 mol percent of the ester mixture into dialkanol amides. The product from the preceding reaction is reacted with a mono lower alkanol amine to convert unreacted ester into mono lower alkanol amide. Both said reactions are carried out in the p~esence of a sodium alkoxide or potassium alkoxide catal~st.
Preferably the di lower alkanol amine used in this embodiment is diethanol amine, the mono lower alkanol amine is mono ethanol amine and the eatalyst is sodium methoxide. Prefer-` ably the esters used in this embod~ment are methyl esters of i ~ 20 alkanoic acids whose aeyl groups have from about lL to about 15 earbon atoms, espeeially where the branched ester includes at lea~t one of: ~1 methyl 2-ethylnonanoate, meth~l 2-ethyl-undeeanoate, and methyl 2-ethyltrideeanoate and of (b) the methyl ester of one or more of the following aeids: undeeanoic acid, 2-methyldeeanoie aeid, trideeanoie aeid, 2-methyl-dodeeanoie aeid, pentadeeanoie aeid, and 2-methyltetradeeanoie ~eid.
.
The present process produces complex mixtures of alkanol amides containing numerous ramifications. The preferr-ed mixtures produced by processing as described herein containvarious numbers of earbon atoms in the aeyl group~ as well as a wide range of ratios of monoalkanol and dialkanol structures.

- eb/ - 20 -.

~5~ )3~
Many of ~he mixtures have uni~ue and valuable properties in regard to vc~rious aspects such as (1) viscosit~ o~ aqueous solutions of the amide, (2~ the melting point of the amides themselves, and ~3) superior washing properties. ;;~
One of the desirable properties of the new composi-tions that can be controlled readily with the present process is viscosity of aqueous solutions. Liquid deter~ent concen- ;~
trates are widely used as in liquid dishwashing detergents and in shampoo. These concentrates preerably are quite viscous.
i 10 The viscosity control aspect provided by certain new amide compositions produced by ~he present process makes it desirable ~;
in some instances to ~eed to the first stage of the present process less than the stoichiometric amount of di lower alkanol amine required to react with all of the portion of the feed ester present which is free of ~ positioned alkyl branches having more than one carbon atom. Thus are obtained mixtures which have various dialkanol amide~monoalkanol amide mol ratios such as 50/50, S5/45, 60/40, 65/35, ~0/30, ~5/25, 8~/20, 85/15, 90/10 and 95/5.
~ . , , ~mide mixtures such as the foregoing are preferably ~' produced by the novel two-stage processing sequence as herein - described using feed esters and amines that produce directly ~ ;
the desired product distribution, however, the useful composi- ;~
tions that now have been discovered can be produced by blendiny in appropriate proportions two or more pure or mixed amides produced by this process or by other~processes. For example, esters ~ith C8, Cll' C12' C13, ~14 or C15 acyl grou~s may be processed separately or in sub-combinations and where desired ~ -, the products blended together or blended with amides from - 30 other sources.
Cextain amide compositions whLch are preferred from a cost-effectiveness point o~ view contain ac~l groups ha~ing : .
' .. ~

O~j - 21 -~051(~3~
fro~ about ll to abou-t 15 carbon atoms. ~mides whose acyl ~roups have 13 carbon ~toms ~re pre~erred because of sup~xi.or yiscosity properties; however, synerc~ls-tic mixtures ~re obtain-ed where thc amides are mixtures wherein some ac~1 groups have ll carbon atoms per group, some acyl groups have 13 carbon atoms and some acyl groups have 15 carboII atoms.
Thus, in ~eneral, mixtures of the present amides are preferr~d wherein C13 acyl groups constitute from about lO to abou~ 90 percent of the total acyl groups present, the balance being Cl1 and Cl5 acyl yroups in relative proportions of from about l:lO to about lO~
Amide mixtures are highly preferred which have from about 25 to about 75 percent Cl3 acyl ~roups with the balance being Cll and Cl5.acyl groups in relative proportions of from about 1:3 to about 3:1. Preferably, from about 40 to about 50 percent of the acyl groups of the amides are Cl3 acyl groups.
~ referably, the amides ~re ethanol amides. Preferred mixtures of di lower alkanol amide and mono lower alkanol amide are characterized in that from about 5 to about 10 mol percent thereof is mono lower alkanol amide whose acyl groups carry.
in the a posi~ion an alk~1 substituent at least two carbon atoms in length. Where low melting amides are desired~ pre~er-ably the amide mixture contains at least.about 50 mol percent d~ lower alkanol amide, mo~e pre~erabl.~ at least about 70 mol percent di lower alkanol amide, especially at least about 90 mol percent o~ di lower alkanol amide. :
The amide compositions of the present invention pro- .
. , ~ide at least comparab}e i~ not superior properties in regard to one performance criteria or another in relationship to con-ventional die~hanol amides or monoethanol amides whose acyl . groups axe obta~ned ~rom natural sourcesO In addition t the .~ . . .
amide~ o~ the present invention hava the further adYantage ~b/ ~ 22 -31 ~5~L03~ ~:
that their ~cyl groups can he produced synth~ticall~ a~ low cost.
PrePerred amicle mixture readily availa~le at low cost particularl~ ~7hen using the present process and preferred starting materials contains from about 10 ~o about 65 mol percent of lower alkanol amide whose acyl groups carr~ a methyl group in the ~ position; however, in especiall~ preferred compositions, from about 12 to about 25 mol percent of the amide mixture of the present invention is lower alkanol amide ~hose acyl groups carry a methyl group in the a position.
Another preferred amide mixture according to the present invention contains from about 8 to about 55 mo~ per-cent mono lower alkanol amide and from a~out g2 to about 45 , mol percent di lower alkanol amide. Fro~ about 2 to about 20 mol percent of the amide mixture is mono lowex alkanol amide whose acyl groups carry in the a position an alkyl substituent .
~ at least two carbon atoms in lenyth. Preferred amides of this ,. ~ ~- .
embodiment are ethanol amides.
~;I, Another preferred amide mixture according to the 20 present invention is ~rom about 25 to about 35 mol percent ;
i monoethanol am~de and ~rom about 75 to about 65 mol percent , diethanol amide. From abou~ 2 to about 20 mol percent thereof is monoethanol am~de whose ac~1 groups carry in the a position ~n ~lkyl substituent at least two carbon atoms in length.
Another preferred amide mixture according to the present invention is about 30 mol~percent monoethanol amide ~nd about ~0 mol percent diethanol amide. From about 2 to about 20 mol percent thereo~ is monoethanol amlde whose acyl ,1 . ' i- ~roups carxy in the position an aLkyl substituent at least t~o carbon atoms in ~en~th.
ii Each o~ ~he alkanol amide mixtures o~ the three i; ~ preceding paragraphs is characterized ln that the acyl groups ''i ' ~ : :

~ 3 ~
,~ - : :~
.. . , ,.. , .. ,, ~". . . . . . . ..

~1~5:~36~
thereof are op~r~ ch~in ac~l ~roups containiny from 11 to about 15 carbon atom~. In adclition~ each of the ~mide mixtures o the three preceding par~graphs ~na~ have one or more o~ ~he ~ollowin~ ~specially preferred limitations~
1 _ The amides thereoE contain 11, 1~ and 15 carbon atoms in thelr acyl groups.
2 - For each 100 parts by weight thereof there are ~rom about 25 to about 40 parts of amide with Cll acyl groups, from about 40 to abou~ 50 parts of amide with C13 acyl groups, ~~
and from about 20 to about 25 parts o~,amide ~ith C15 acyl , , groups.
3 - From about 10 to about 65 mol percent of the A mixture is lower alkanol amiae whose acyl groups carry a: methyl group in the ~ position.
' 4 - From about 12 to about 25 mol percent of the ,. . . .
mixture is lover alkanol amlde whose acyl groups carry a methyl group in the a position.
, As no~ed above, the compositions of this invention can be used with a wide variety of organic detexgent surfact-ants, Included in the category are thoqe classed in the art as anionic det,ergents, cationic detergents, nonionic detergents, ampholytic (i.e.~ amphoteric) detergents and zwitterionic . detergents, and any suitable mixture of' two or more of these ;~ , (whether from the same class or from di~fexent classes~. The anionic surface-active compounds are yenexally described as ~, compounds which contain hydrophilic and lyophilic groups in .. . .
their molecular structure and which ionize ln an aqueous medium to glve anions contaln~ng the lyophilic group. Typical of ~, ,......................................................................... .
~` these compounds are the alkali metal s~lts or or~anic sulfonates 30 or sul~ates, such as the alkall metal alkyl aryl sulfonates and the alkali metal salts o~ sul~ates of straight chain pri- ~
- .
mary alcohols~ Sodium dodecylbenzene sul~onate and sodium ~ .:
.
cb/ - 2 4 ~ 05~3~
l~uryl sulfate are typic~l ~xampl~s of t:}leSC anionic surface-active compound~ ~nionic synthetic det~r~cnts). For a fur~her ampllfication of anionic organlc deteryents which can be successfull~ combined with the amides in accordance with this inyentio~, re~erence should ~e had to U. S. Patent No. 3,422,021, particularly the passage extending from Column 11, line 4 through Column 12, line 15, including the references therein cited~
The cationic detergents are those which ionize in an aqueous medium to give cations containing the lyophilic group.
Typical of these compounds are the quaternary ammonium salts which contain an alkyl group of about 12 to about 18 carbon atoms, such as lauryl benzyl dimethyl ammonium chloride.
Compounds of this nature are used in detergent formulations ~or special purposes; e.g., sanitizing and fabric softening~
Nonionic surface-actiye compounds are ge~e~ally des-cribed as compounds which do not ionize in water solution.
Often times these possess hydrophilic characteristics by yirtue of the presence therein of an oxygenated chaln ~e.g., ~- 20 a poLyox~ethylene chain), the lyophilic portion of the mole-cule being derived from fatty acids, phenols, alcohols, amldes or amines. Exemplary materials are the poly-(ethylene oxide) condensates of alkyl phenols ~e.g., the condensation product ~ormed from one mole of nonyl phenol and ten moles of ethylene `
oxide~, and the condensation products of aliphatic alcohols and ethylene oxide le.g./ the condensation pxoduct formed from l mole of trideaanol and 12 moles of ethylene oxide).
~eference should be had to U. S. Patent No. 3,422,0~1, especially the passage extending ~rom Column 12, line 16 through Column ~ -13, line 26 where a fairly extensive discussion and exemplificati~
o~ nonlonic s~nthetic detergents is set forth. The nonionic ~ynthetic detergents set ~orth in that passage can be success~

"
ob~ ~ 2 5 ~L0~ 3~ ~
fully used in accordance witll this invention.
The ampholytlc sur~ctants are compounds havlng both anionic and cationi.c groups in the same molecule.~ ~xemplary of such materials are deri~atiyes of aliphatic amines which - contain a long chain of about 8 to about 18 carbon atoms and an anionic water solubilizing group, e.g.~ carboxysulfo, sulfo, or sulfato. Examples of ampholytic detergents are sodium-3-dodecylaminopropionate, sodium-3-dodecylaminopropane sulfonate, sodium-N-methyl taurate, and related substances such as highex alkyl disubstituted amino acids, betaines, thetines, sulfated long chain ole~inic amines, and sulfated imldazoline derivatives.
Zwitterionic synthetic detergents are generally regard~
ed as derivatives of aliphatic quaternary ammonium compounds in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from , . . .
about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, or sulfato. Examples ~-of compounds falling within this definition are 3-~N,N-dimethyl-N-hexadecyl ammonio)-propane-l-sulfonate and 3-~N,N-dimethyl-N-hexadecyl ammonio~-2-hydroxypropane-1-sulfonate. For a still ~uxther appreciation of surface-active compounds (synthetic detergents) which can be employed in the practice of this nyention re~erence may be h~d, or ex~mple, to the disclosures of U. $. Patent 2,961,409 and French Patent 1,398,753.
For a very extensive disclosure of surfactants in general, see U. S. 3,526,592 and the various U~ S. Patents referred to therein.
Finished detergent formulatio~ of this invention :.
ma~ contain minor amounts of other commonly used materials in order to enhance the effectiveness or attractiveness of the product. Exemplary of such materials are soluble sodium : .

cb~ - 26 ~0~1~3~
~arbox~me-thyl cellulose or other soil redeposition inhibi.torsi per~ume; inorcJanic salts sucli ~s sodium chloride, sod.ium sul- ..
fate; alum; fluorescers; d~es or pigments; briyhtenlng agents; ~.
enzymes; water; alcohols; builder additives, such as the water-soluble salts of ethylenediaminetetraacetic acid, N-~2-hydxoxy- -ethyl)-ethylene-diaminetriacetic acid, nitrilot~iacetic acid, .
N-(2-hydroxyethyl)-nitrilodiacetic acid, carboxymethoxy succinic acid, citric acid, and pH adjusters, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and potassium carbonate. In liqui.d detergent formulations of this invention, the use of hydrotropic agents may be found effica-cious. Suitable hydrotropes include the water-solu~le alkali metal salts of toluene sulfonic acid, benzene sulfonic acid, and xylene sulfonic acid. Potassium toluene sulfonate and sodium toluene sulfonate are p~eferred for this use and will normally be employed in concentrations ranging from about 2 :
: to 10 percent by weight based on the total composition. ;~
: . .It will be apparent from the foregoing that the compositions of this invention may be formulated according to any of the ~arious commercially desirable forms. For example, - the formulations of th~s.inventLon may be provided in granular ~orm, in liquid form, in tablet form or in the form of flakes : :
OX powders. . ~
~, .
The relative proportions and absolute quantities of;:
the several ingredients of the finished compositions of this:~
invention are susceptible to variation and in most cases will vary depending upon such factors as the nature of the particular :.
ingredients being utilized, the end use for which the composi-tion is intended to be put, the relative costs.of the ingred-ients, ~nd the li~e. For example, the total concentration of the detergent formula~ions o~ this invention in w~ter will noxmally range below about 0.15 pexcent by weight although it . :
.~

ck~t ~ 2 7 r ~ ~ .
... . . . .

~OS1~3~ ~
is entil~ely f~asible to util.ize hi~her concen~r~tions ~llere the circumstances w~rrant or justify the use of higher concentra-tions In most cases the a~ueous w~shing solutions of this invention will contain from about 0.05 to about 1 weight percent combined organic detergent surfactant(s~ and amidei although concentrates may range up to the limit of solubility. The preferred compositions of this invention are phosphorus-free when desired although it may be desired to include therein normal or reduced quantities of conventional phosphorus-containing materials such as sodium tripolyphosphate, tetra-sodium pyrophosphate, salts of substituted methylene diphosphonic containing materials such as sodium tripolyphosphate, tetra-sodium pyrophosphate, salts of su~stituted methylene diphosphonic acids, long chain tertiary phosphine o~ides, or the like.
,! The invention is not to be limited to any particular ! method of mixing the amide and the detergent. The amide may be mechanically mixed in, crutched in the detergent in the form of a slurry, or dlssolved in a solution of the detergent.
In addition, the amide system may be admixed with the deter-gent in any of the forms in which the detergent is manufactured, as well as being added s~multaneously or separately to an aqueous solution. In any event, the present amide system is intended to be used with the detergent at the time of applica- ~ ~
i tion as a cleansing agent. `
It is evident that the present process and composi- ~
.
tions are disclosed as containing numerous variations and pro-portions of the materials in regard to: (A) proportions of materials of the three structures: (1) unbranched at the position, t2) ~-meth~l branched, t3) a~ethyl, a-propyl and higher alkyl,~ positioned branched, as well as of ~B) the ratio of (~1) dl alkanol ~mine fed in the first st~ge to monoalkanol amine fed in the second stage), as well as of (C~ numbers of cb~ . 28 - `~
'' - ' ,,, , , :'" ~

1~5.~L~30 carbon ~toms in ~(1) acyl groups and (2) -the alkanol groups) o mixtures, as well as o~ (D) oryanic detergent suxf~ctant and other adjuv~nts. In the interest of ~onciseness, the various factors are set ~orth separately; however, it is intended ~-that the pre~erred cri~eria giv~n for the facto~s operate individually as well as collectively and that therefore cross- -reading of the various criteria is contemplated and is hereby specifically disclosed.
The following examples indicate preferred embodiments and aspects of the present invention.
EXAMPLE I
Preparation of C13 ~mides ~9~1 ratio~
To a 200 ml creased flask equipped with a vacuum pump, an agitator, an oil bath for temperature control, and a condensate collector for methanol liberated by the esters, was added 100 grams (0.438 mol? of mixed methyl Cl3 ester contain~ng:
Wt. Pe~cent meth~1 tridecanoate 80 methyl a-methyl dodecanoate 14 methyl a-ethyl undecanoate i methyl a-prop~l dec~noate methyl a-butyl nonanoate, etc. 6 ., The esters were produced by reacting dodecene~l with CO in the presence of methanol and with cobalt carbonyl c~talyst. As is evident, 80 percent of the ester has straight chain C13 acyl groups.
1 To the flask was also added 41.4 gxams ~0.394 ~ol) J- of diethanol amine and 8.4 grams of a 25 wt. percent solution .~ .
o~ sodium methoxide catalyst in methyl alcohol. The amount of sodium methoxide was 2.10 ~rams (0.0388 mol).
The syst0m was evacua~ed to 32 mm ~g absolute pre-ssure and heated to about 60C, and held under these conditions ., , .:,: . . : ..
.. . .
~ 29 -.~

, . ... ~ , ~, . . . . . . .. . . .... .. .

i~5103(~ ~ ~
for 20 minu~s. ~`
Th~n 2 . 7 c3rams ~0.044 mol) of monoethanol ~mine was added and the system wa~ heated to lOO~C and held at that temperature ~or 39 minutes at 32 mm Hg absolute pressure.
The product weighed 127.5 grams. ~;
After the reaction, the catalyst was neutraliæed b~
adding a stoichiometric amount ~f g]acial acetic acid calculated on a basis of the sodium methoxide fed.
A yield of 98.7 percent alkanol amide was obtained.
In this example, the mol ratio of dialkanol amide xelati~e to the monoalkanol am~de was about 9/1 Product impurities were ~wt. percenk):

Ester methyl tridecanoate 0.07 methyl ~-methyl dodecanoate 0.19 methyl higher alkyl su~stituted esters 0.~0 Amine Dlethanol amine 4~2 20Monoet~anol amine 2.
. ~ ~
j~ EXAMPLE I~

Preparation of C13 Amides (9.5/1 Ratio~
- . .
Example I was repeated using 100 grams ~0.438 mol) of the C13 ester, 43.7 grams ~0.416 mol) of diethanol amine, 2 70 grams ~0.044 mol~ of mo~oethanol amine, a~d 8.3 grams of the 25 wt. percent solution o~ sodium methoxide in methyl aIco-hoL, The amount of sodium methoxide was 2.075 grams ~0.0384 ~oll. The mol ratio o~ catal~st to ester was 0 0877.
7 , The first reaction was for about 1~ ~inutes at about ',~7: ~ 30 62-64C and 30 mm o Hg. The second stage reaction time was ;~
40 minutes at 104-105C and 30 mm of Hg.

The product weighed 126.5 grams.
~ In this exampLe, the mol ratio o~ dialkanol amide -to monoalkanol amide was about 9.5/1.
7 ' cb/ 30 EX~MPLE III
Preparation of Cl~ ~mides ~9.5/1 Ratio) Example II was repeated using 8.~ grams of catalyst solution ~0.386 mols CE~30Na, 0.0885 mol xatio of catalystt4 ester3.
The pressure was atmospheric pressure. Temperature was 56-105C for total time of 35 minutes. The time of addi- -tion of the monoethanol amine was not noted; however, the ratio of the reaction times was about the same as in the pre- ;
ceding examples.
The product weighed 129.00 grams.
In this example the mol ratio of dialkanol amide to :
monoalkanol amide Nas about 9.5/1.
. . EX~MPLE IV
' .Preparation of. C13 Amides ~7/3 xatio~.
i Example I was repeated using 32.5 gxams ~Ø309 mol~
of diethanol amine, 11.5 grams (0.109 mol~ of monoethanol amine and 8.6 grams o~ catalyst solutLon ~catalyst content 2.15 grams - Q.0398 moL) l 20 ~ The first sta~e reaction time was 9 minutes at about . y ~, ~0C and at 30 mm of Hg absolute pxessure. The second stage , . . .
., xeaction time was 46 minutes at about 105C and at 30 mm of Hg absolute pressure.
124 Grams of pxoduct was obtained which was oYer 9o percent alkanol amide.
The mol ratio o~ dialkanol amide to monoalkanol a~ide ~as about ~/3. . .
EXAMPLE V
,~ : . . . . ..
~ Preparation.o~. Cl.3 Amides. ~5~5 Ratio~
j 30 ~xample I ~as repeated using 23 grams ~0,21~ mol) ~ ~.
. of dlethanol amine, 13.~ ~rams (0.223 mol): oY monoethanol ~lne and 8.6 grams o~ ca~alyst solution (2,15 grams - O,0398 mol), :
cb/ - 31 -.

~ 30 Th~ fir~t 9tag~ reac~lon was 13 minutes at abou~ ~O~C
and ~t 30 mm o~ IIcJ absolute pressure. The second stage reaction was ~4 minutes at about 105C and at 30 ~n Hg absolute pressure.
116 Grams of pro~uct was obtained.
The mol ~atio of dialkanol amide to monoalkanol amide was about 5/5.
EXAMPLE VI
- Preparation of Cll Amides ~9/l Ratio) Example I was repeated using mixed methyl Cll ester 10 containing: ?~
Wt. Percent methyl undecanoate 74.3 methyl ~-methyIdecanoate 16 methyl ~-ethyl nonanoate methyl ~-propyl octanoate methyl a-butyl heptanoate, etc. 9.5 ` This was produced by reacting decene-l with CO in .
`~ the presence of methanol and with cobalt carbonyl c~talyst.
lO0 Grams ~0.50 moll of ester, 47.5 grams ~0 452 ;
' 20 mol~ of diethanol amine, 3.10 grams (0.0507 mol) of monoethanol amine and 11.5 grams of 25 p rcent sodium methoxide solution in methyl alcohol ~2.30 grams cata~yst - 0.0426 mol~ were .
aharged to the flask.
The first stage reaction was ~or 20 minut~s at 60-65~C and at about 32 mm Hg absolute pressure. The second ;;
stage reaction was for 41 minutes at about 105-106C and at 29 mm Hg absolute pressura.
The mol ratio of dialkanol amide relative to mono-alkanol amide Was about 9~1. The product weighed 129 grams.
~ EXAMPLE VII ;~
Pxepa~ation o~ Cl5 Amides ~9/1 Ratio~
Example ~ was repeated using mixed methyl Cl5 ester contain~ng:

:, . . .
cb/ - 32 -, . , ~ ;

1051030 Wt, Pcrcent ~;
methyl pentadecanoa~e ~4.2 methyl ~~methyl tetraclecanoate 17,0 ~:~
methyl ~-ethyl tridecanoate methyl ~-propyl dodecanoate . ~ ~
methyl ~-but~l undecanoate, etc. 8.8 :-.
100 Grams ~0.39 mol). of ester, 36.9 grams ~0.351 mol) o~ diethanol amine, 2.~0 grams (0.039 mol) of monoethanol ~ ~
amine and 7.5 grams of 25 percent sodium methoxide solution .: :
in methyl alcohol (1.875 grams - 0.0347 mol) were charged to ~:
the ~lask.
The first stage reaction was ~or 20 m~nutes at 63-64C and at about 30 mm ~g absolute pressure. The second .. . .
~ stage reaction was for 40 minutes at about 105-10~C and at `! 30 mm Hg absolute pressure The mol ratio of dialkanol amide relative to mono-alkanol amide was about 9/1. The product weighed 123.5 grams.
: EXAMPLE VIII
Example VI was repeated with a diethanol amlne!mono-ethanol amine ratio proportioned to provide a Cll amide pro-I duct with a mol ratio of diethanol amide to monoethanol amide i o~ about 7/3.
:'. . . .
EXAMPLE IX
Example VI was repeated with ~ dieth~nol amine~mono- ~.
.: :
~; .ethanol amlna ratio proportioned to provide a Cll amide product ~ .
~ . .
~ with a mol ratio of diethanol amide to monoethanol amide of ..
, ¦ about 5/5.
EXAMPLE X
Example VII was repeated with a diethanol amine/mono- ~
ethanol amine ratio proportioned to provide a C15 ami~e product . :;. :
:with a mol ratio of dieth~nol amide to monoethanol amide of ~bout 7~3.

c~ 33 .
, .

3LV510~0 EX~MPLE XI
Example VII was ~epea~ed with a diethanol amine/mono eithanol amine ratio proportioned to provide a Cl5 amide product with a mol ratio o~ die~hanol amide to monoe~hanol amide o~
about 5/5.
EX~MPLE XII
The following mixea ester composition was reacted with a diethanol amine in an amine/ester mol ratio of slightly greater,than 1/l and samples taken every fifteen minutes to determine reaction rates for the various esters. Rate data were taken showing that the straight chain or normal ester ~ . -,~ methyl tridecanoate was more reactive than the ~a-methyl) ester ,~ which in turn was more reactive than the a-ethyl, a-propyl, etc. esters. '~
' , Wt. Percent ~ methyl tridecanoate ~5 ,, methyl ~methyl dodecanoate21.5 methyl ~-ethyl undecanoate methyl a-propyl decanoate ~' 20 methyl a-butyl nonanoate, etc, 3,5 ,~

'~ ~j EXAMPLE XIII ' ~' , Another portion o~ the ester as used in Example XII
, was disttlled to provide an overhead ~raction and a ~ottoms . , :
', fxaction. ,~
.. . . .
I The bot,toms ~raction had the following analysis ' , ,' and was reacted as in Bxample XII ~iving similar relative rate '-~
data for the variou~ components. - ,,, ~, . . ~ ,. ..
; ' Wt. Percent '~l methyl tridecanoate 96.0 ' , ,~, 30 methyl ~-meth~l dodecanoate 3.66 '1 , ' . ' 'l methyl ~-ethyl undecanoate methyl ~ propYl decanoate meth~ butyl nonanoate, etc, 0.~4 , ~ .:
. ~ .
~ ~b~ ~ 34 ~ , :;' .. . :
.

3~
This compo~ition can provlde a synthetic dialkanol amide o~ high contcnt of dialkanol amide ~9Q-98 percent) when subjected to a second step reaction with merely a small quantity of monoalkanol arni~e.
This is an excellent product where the cost of dis-tillation is acceptable but usually one prefers to avoid such costs using the undistilled ester.
EXAMPLE XIV
The overhead fraction from Example XIII had the following analysis and was reacted as in Example XII showing similar relative rate data for the various components.
Wt. Percent methyl tridecanoate 22.1 ; methyl -methyl dodecanoate60.0 - methyl a-ethyl undecanoate methyl a~propyl decanoate methyl -butyl nonanoate 1~.8 This illustrates ester compositions which produce amides whose acyl groups have a high percentage of ~ positioned ; ;~
alkyl group substitution including substitution by alkyl group~
having two or more carbon atoms per alkyl group, Although these compositions have desirable per~ormance characteristics, unless the bottoms fraction o~ Exarnple XIII has premium value for other uses, it is usually preferred to use the undistilled compositions which provide their good properties without involving the distillation expense. The overhead composition of this Example would be o~ little value as a feed for a base catalyzed amidation process to produce amides without the teach-. 1 ings of the present invention.
; 30 EXAMPLES XV-XXIV
. . .
, Amide composit~ons o~ Examples I and IV~XI were com-., . : ..
bined in various proportlons as set forth in Table ~ to provide ~ ~
a wide variety of mixtures in regard to ~1) ratio o~ diethanol ' ~ amlde to monoethanol amide and ~2) molecular weight. The com-', : ' ~ ' cbf - 3 5 positions wer~ blend~d with oxganic d~terg~nt surfactants and tested for washing pcrfo~mance in a~ueous solutions in s~veral standarcl ways. The da~a obtained are set ~orth in Table II.
V ~ t .
Viscosity of aqueous solutlons containiny ~he mixed amide compositions of subsequent examples was measured using a ~Iaake Roto Visco rotary viscosimeter. Measurements were made -~
at 25C and are tabulated herein. Viscosity is expressed as . centipoises per second ~CPS). ~ ;
For this test, 15 wt. percent solutions of organic detergent surfactant and amide in water were made. The weight ;~
ratio of surfactant to amide was 11/4. The surfactant used was a conventional LAS (linear alkyl benzene sulfonate) (Ultrawet ~ K manufactured by Arco Chemical Co.l. ~here this hAS is used as a 36.2 weight percent solution, the amount of surfactant used is on dry basis.
This test is used to identify amide compositions -l that provide a desirably high viscosity of liquid concentrate under standard conditions, I~ general~ the higher viscosity 20 compositions are more desired. ~he viscosity factor as used ;~
herein is the ratio of the viscosity o~ the test solution : ,, . .:
relative to the viscos~ty o~ a standard amide solution.
Thus large values of visco~ity factor are desired. The stand-ard amide used was made into a similar 15 percent soIution with a llJ4 ratio of surfactant to amide using th~ same LAS
as sux~actant and, as amide, a natural source 90 percent lauric-10 percent myristic coconut oil diethanol "super"
amide ~AA62 X manu~actured by Stepan Chemical Co.), ~etting Tlme This is a Draves Wet~ing Test as descr~bed by Harris, J C " ~'Detergenc~ Evaluation and Testing", Intersclence, 1954, p 40 .
.
c~ - 36 -:

3~ ~
Wettiny tim~ is expressed in seconcls ~o~ a stand~rd hank of striny usiny a standard solukion of each amide o~ a concentration similar to that used by the housewi~e in washing.
Each test solution was an aqueous solution oE 0.05 wt. percent total active content wherein the active was sodium lauryl sulfate and amide in a 9/1 weigl~t ratio. Water used was distilled water of 0 ppm hardness. Various alkanol amide compositions including a solution containing AA-62X were test-ed and results tabulated.
`~ 10 M ~
This is a standard diswashing test J. Am. Oil Chem.
Soc. 43, 576 (1964) using small plates. Three separate sets ~;~
of tests were made in water o~ 0, 50 and 150 ppm of hardness ICa/Mg mol ratio 3/2). Tests were made at 45 using solutions ; containing 0.045 wt. percent active. The actives were tested ~, . .
in ternary mixtures containing LAS, AES and amide in 60/3QJ10 weight ratio. The LAS used was Ultrawet ~ K as used in the viscosity tests. The AES wa~ ~lcohol ethoxy sulfate ~lfonic 1412,4 of Continental O~l Co.).
Ross-Miles Test This is a standard foam volume and stability test as described by Harris, J. C., "Detergency Evaluation and Testing", Interscience 1954, p. 47. The test was made at 40C
j using aqueous solutions containing 0.050 wt. percent total active, with foam heiyhts measured in millimeters at the start o~ the test and also 5 minutes later.
The actiYe solution used was a ~1 SLS/amide solution ln distilled water as used fox the we~ting ~me test.
; ~XAMP~E X~
This composi~ion contained a mixture of dialkanol amide and monoalkanol a~ide in appraximatel~ a 9/1 mol ratio Cll, C13 and C15 amide weight ratios of 40/40~20 , . ' ' ~b/ 37 - .
. , , ' . . .

~ 0~ ~3~
formed by blending p~oduct o~ Llxamples I t V~ ana VII- This is an excellent composition with a melting point below 25C.
It is an easily handled li~uid a~ room tempexatures. It has the bene~i~ of being a low cost synthetic source material which is at least comparable to and in some respects slightly better than the natural source coconut oil diethanol super amide used as a standard. It is a preferred composition in many ways. Blendillg data for this and subsequent examples ;
are tabulated in Table I. Performance data for this and subsequent examples are tabulated in Table II.
.
EXAMPLE XVI
This amide mixture composition had a 9/1 mol ratio ~ -of dialkanol amide to monoalkanol amide and Cll, C13 and C15 ~ -amide weight ratios of 25/50/25 and was formed by blending : .
product from Examples I, VI and VII. Like the product of Example XV, this composition has a melting point below 25C
,~ . ... ~
providing a highly desired product that can he handled as i a liquid at room temperature. Performance-w~se this com-................... .. . .
pOSition is superior to the natural source coconut oil deriv- ~ ;
o ed diethanol super amide in ~irtuall~ all performance aspects ~, .
, tested. The viscosity was more than 25 pexcent higher ~be~ter~
~ - . . .
~or this amide mixtuxe in comparison to the AA62-X dialkanol super amide. It was superior to the natural source super , ~mide in the wetting test and in the Miniplate washing test.
It i5 a preferred composition in many respects.
EXAM~LE XVII
This amide mixture composition had approximately a ' 9/1 mol ratio of dialkanol amide to monoalkanol amide and C
j~ C13 and C15 amide weight r~tios of 15/57/28. This composition ~0 provided outstanding results in the viscosity test. The vis~
~' ~ cosit~ w~s higher than the standard by a factor o~ 1.5 ` cb~ ~ ~ 38 ~ ~
: - -: - .
'. .~ - : ' , ' ' .: .
' ' ' . . ': ' ~05~ 3~
EXAM~LE XVIII
This amicle mix~ure composition had approximately a 9~1 mol ratio of dialkanol amide to monQalkanol amide and Cll, C13 and C15 amide weight ratios o~ 10/60/30. This com-- position provided results similar to those o~ Example XVII
and had an even higher ~iscosity factor of 1.6:1.
EXAMPLE XIX
This amide mixture composition had approximately a . 7/3 mol ratio or dialkanol amide to monoalkanol amide and C~
C13 and C15 amide weight ratios of 40/40/20. As shown in the tabulation, this composition was outstanding in all the per-formance tests, particularly viscosity, wetting, Miniplate and Ross-Miles and represents a particularly preferred composition.
EXAMPLÆ XX
This amide mixture composition had approximately a 7/3 mol ratio of dialkanol amide to monoalkanol amide and Cll, C13 and C15 amide weight ratios of 25/50/25, This composition was outstanding in the viscosity and Miniplate tests. It is a preferred composition.
EXAMPLE XXI
. .
- This amide mixture composition had approximately a

5/5 mo? ratio o~ dialkanol am~de to monoalkanol ~mide and Cll, C13 and C15 amide weight ratios of 40/40/20. This composition provided outstanding per~ormance in the Miniplate test and ` gave high viscosity readings. The comparatively high melting j point makes this composition particularly useful in instances ~-here high viscosity is desired and the factor of li~uid ; `~
~,~ handling at room temperature is of lesser importanoe.
J EXAMPLE XXII
~ , , This amide mixtu~e Gomposition had approximatel~ a 5/5 mol ratio of dialkanol amide to monoalkanol amide and Cl~

- C13 and C15 amide wei~ht ratios of 25~50/25. This composition ~ -. . ~ . .
:
c~ 39 - -.

~L~35~L0 30 provi.ded pc~r~lcularly ou~standing results i.n the viscosity and Miniplate t~sts. Where hi~h viscosity and high mlniplate washinq f~ctors are desired and the actor of liquid handliny :~
at room ~emperature is less impor~ant, this is a particularly ~ :~
Yaluable and suitable composition.
EX~MPLE XXIII
- This amide mixture composition was the 7/3 C13 product oE Example IV. It is included in the performance :
data tabulated to show the high viscosity (factor ~ 2~2) pro~
vided by diethanol amide/monoethanol amides having C13 acyl ~roups. Similar viscosity tests of 7/3 C11 and 7/3 C15 samples ~, provided viscosity factors of about 1.0 but when the Cll and .
C15 amiaes were combined with the C13 amide, a synergistic .
~, combined viscosity result was obtained as shown by Example XX. :
.~, EXAMPLE XXIV
I This is a comparative Example using a conventional ;, natural source diethanol lauric-myristic.super amide ~A-62X 1.

`! of Stepan Chemical Co.). This product is substantially 100 .. . . . .
percent diethanol amide of which 90 percent is lauric ~C12) I ;20 and 10 percent is myristic ~C14?. It requires a narrow cut of coconut oil materials rich in the more desirable acyl.
groups of coconut oil. As is evident, the typical amide com-positions of the present invention having synthetic acyl groups are at least equal to this conventional natural source material in most performance aspects which is surprising in itself while each O.L the present typical compositions is decidedly -a~d unexpectedly superior to the natural source material in at least one of the performance aspects. .

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Claims (58)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for producing alkanol amide mixtures which comprises:
reacting a di lower alkanol amine with a mixture of lower alkyl esters of aliphatic monocarboxylic acids whose acyl groups contain from about 8 to about 20 carbon atoms, said mixture being character-ized in that from about 2 to about 20 mol percent of said ester mixture is branched ester in which the acyl groups carry in the .alpha. position an alkyl substituent at least two carbon atoms in length, said branched ester being substantially unreactive with said amine, the amount of said amine employed being sufficient to convert at least 10 mol percent of the ester mixture into di lower alkanol amide;
and then reacting the product from the preceding reaction -with a mono lower alkanol amine to convert unreact-ed ester into mono lower alkanol amide, both said reactions being carried out in the presence of a base catalyst.

2. The process of claim 1 wherein the mol ratio of dialkanol amine to lower alkyl esters employed in the first reaction doe? not exceed about 1.2:1.

3. The process of claim 1 wherein the mol ratio of dialkanol amine to lower alkyl esters employed in the first reaction falls in the range of about 0.4:1 to about 1:1.

4. The process of claim 1 wherein the amount of mono-alkanol amine employed in the second reaction is not sub-stantially in excess of the amount required to react with said unreacted ester.

5. The process of claim 1 wherein the mol ratio of monoalkanol amine to said unreacted ester in the second reaction falls in the range of about 0.9:1 to about 1.2:1.

6. The process of claim 1 wherein the mol ratio of di-alkanol amine to lower alkyl esters employed in the first reaction falls in the range of about 0.5:1 to about 0.9:1 and the mol ratio of monoalkanol amine to said unreacted ester in the second reaction is in the order of about 1:1.

7. The process of claim 1 wherein from about 5 to about 10 mol percent of said mixture is branched ester in which the acyl groups carry in the a position an alkyl substituent at least two carbon atoms in length.

8. The process of claim 1 wherein said mixture is further characterized in that from about 10 to about 65 mol percent of said mixture is branched ester in which the acyl groups carry a methyl group in the .alpha. position.

9. The process of claim 1 wherein said mixture is further characterized in that from about 12 to about 25 mol percent of said mixture is branched ester in which the acyl groups carry a methyl group in the .alpha. position.

10. The process of claim 1 wherein the esters are esters of aliphatic monocarboxylic acids whose acyl groups have from about 11 to about 15 carbon atoms.

11. The process of claim 1 wherein the esters are a mixture of esters of aliphatic monocarboxylic acids whose acyl groups have 11, 13 and 15 carbon atoms.

12. The process of claim 1 wherein from about 40 to about 50 percent of the esters reacted have C13 acyl groups.

13. The process of claim 1 wherein the termperature of each of said reactions is in the range of about 25°C to about 150°C.

14. The process of claim 1 wherein the temperature is in the range of about 40°C to about 75°C for the first reaction and in the range of about 75°C to about 125°C for the second reaction.

15. The process of claim 1 wherein the temperature employ-ed in the second reaction is higher than the temperature employ-ed in the first reaction.

16. The process of claim 1 wherein the catalyst is an alkali metal, an alkali metal alkoxide or an alkali metal amide.

17. The process of claim 1 wherein the catalyst is an alkali metal alkoxide.

18. The process of claim 1 wherein the catalyst is sodium methoxide.

19. The process of claim 1 wherein the lower alkanol amines reacted have from 2 to about 4 carbon atoms per alkanol group.

20. The process of claim 1 wherein the lower alkanol amines reacted are diethanol amine and monoethanol amine, respectively.

21. The process of claim 1 wherein the lower alkanol amines reacted are diisopropanol amine and monoisopropanol amine, respectively.

22. The process of claim 1 wherein the esters reacted are methyl, ethyl, propyl, or butyl esters.

23. The process of claim 1 wherein the esters reacted are methyl esters,

24. The process of claim 1 wherein in the first stage the di lower alkanol amine is added intermittently or contin-uously to the ester-containing reaction mixture and in the second stage the mono lower alkanol amine is added inter-mittently or continuously to the amide-containing reaction mix-ture from the first stage.

25. The process of claim 1 wherein the esters are methyl esters, the di lower alkanol amine is diethanol amine, the catalyst is sodium methoxide, the reaction temperature of the first stage is from about 40°C to about 75°C, the mono lower alkanol amine is monoethanol amine, and the reaction temperature in the second stage is from about 75°C to about 125°C.

26. A process for producing alkanol amide mixtures which comprises:
reacting a di lower alkanol amine with a mixture of methyl esters of aliphatic monocarboxylic acids whose acyl groups contain from about 8 to about 20 carbon atoms, said mixture being char-acterized in that from about 2 to about 20 mol percent of said ester mixture is branched ester in which the acyl groups carry in the N position an alkyl substituent at least two carbon atoms in length, said branched ester being substantially unreactive with said amine, the amount of said amine employed being sufficient to convert at least 40 mol percent of the ester mixture into di lower alkanol amide; and then reacting the product from the preceding step with a mono lower alkanol amine to convert unreacted ester into mono lower alkanol amide, both said reactions being carried out in the presence of a sodium alkoxide or potassium alkoxide catalyst.

27. The process of claim 26 wherein the di lower alkanol amine is diethanol amine, the mono lower alkanol amine is monoethanol amine and the catalyst is sodium methoxide.

28. The process of claim 27 wherein said esters are methyl esters of alkanoic acids whose acyl groups have from about 11 to about 15 carbon atoms.

29. The process of claim 26 wherein said branched ester includes at least one of: methyl 2-ethylnonanoate, methyl 2-ethylundecanoate, and methyl 2-ethyltridecanoate; and wherein said ester mixture includes the methyl ester of one or more of the following acids: undecanoic acid, 2-methyldecanoic acid, tridecanoic acid, 2-methyldodecanoic acid, pentadecanoic acid, and 2-methyltetradecanoic acid.

30. A mixture of mono and di lower alkanol amides in which the acyl groups are open chain acyl groups containing from about 8 to about 20 carbon atoms, said mixture being characterized in that at least 10 mol percent thereof is di lower alkanol amide and in that from about 2 to about 20 mol.
percent of said mixture is mono lower alkanol amide whose acyl groups carry in the .alpha. position an alkyl substituent at least two carbon atoms in length.

31. A mixture according to claim 30 wherein substantially all of said amides have acyl groups containing from about 11 to about 15 carbon atoms.

32. A mixture according to claim 31 wherein substantially all of said groups contain 13 carbon atoms.

33. A mixture according to claim 30 wherein said amides are ethanol amides.

34. A mixture according to claim 30 characterized in that from about 5 to about 10 mol percent of said mixture is mono lower alkanol amide whose acyl groups carry in the .alpha. position an alkyl substituent at least two carbon atoms in length.

35. A mixture according to claim 30 further character-ized in that it contains at least about 50 mol percent di lower alkanol amide.

36. A mixture according to claim 30 further characterized in that it contains at least about 70 mol percent di lower alkanol amide.

37. A mixture according to claim 30 further characterized in that it contains at least about 90 mol percent di lower alkanol amide.

38. A mixture according to claim 30 further characterized in that from about 10 to about 65 mol percent of the mixture is lower alkanol amide whose acyl groups carry a methyl group in the .alpha. position.

39. A mixture according to claim 30 further characterized in that from about 12 to about 25 mol percent of the mixture is lower alkanol amide whose acyl groups carry a methyl group in the a position.

40. A mixture of from about 8 to about 55 mol percent mono lower alkanol amide and from about 92 to about 45 mol percent di lower alkanol amide, the acyl groups of the amides being open chain acyl groups containing from about 11 to about 15 carbon atoms, said mixture being characterized in that from about 2 to about 20 mol percent thereof is mono lower alkanol amide whose acyl groups carry in the .alpha. position an alkyl substituent at least two carbon atoms in length.

41. A mixture according to claim 40 wherein the lower alkanol amides thereof contain 11, 13 and 15 carbon atoms in their acyl groups.

42. A mixture according to claim 41 wherein, for each 100; parts by weight thereof, there are from about 25 to about 40 parts of amide with C11 acyl groups, from about 40 to about 50 parts of amide with C13 acyl groups and from about 20 to about 25 parts of amide with C15 acyl groups.

43. A mixture according to claim 40 wherein said amides are ethanol amides.

44. A mixture according to claim 40 further characterized in that from about 10 to about 65 mol percent of the mixture is lower alkanol amide whose acyl groups carry a methyl group in the .alpha. position.

45. A mixture according to claim 40 further characterized in that from about 12 to about 25 mol percent of the mixture slower alkanol amide whose acyl groups carry a methyl group in the .alpha. position.

46. A mixture of from about 25 to about 35 mol percent monoethanol amide and from about 75 to about 65 mol percent diethanol amide, the acyl groups of the amides being open chain acyl groups containing from about 11 to about 15 carbon atoms, said mixture being characterized in that from about 2 to about 20 mol percent thereof is monoethanol amide whose acyl groups carry in the a position an alkyl substituent at least two carbon atoms in length.

47. A mixture according to claim 46 wherein the ethanol amides thereof contain 11, 13 and 15 carbon atoms in their acyl groups.

48. A mixture according to claim 47 wherein, for each 100 parts by weight thereof, there are from about 25 to about 40 parts of amide with C11 acyl groups, from about 40 to about 50 parts of amide with C13 acyl groups and from about 20 to about 25 parts of amide with C15 acyl groups.

49. A mixture according to claim 46 further characterized in that from about 10 to about 65 mol percent of the mixture is ethanol amide whose acyl groups carry a methyl group in the .alpha. position.

50. A mixture according to claim 46 further characterized in that from about 12 to about 25 mol percent of the mixture is ethanol amide whose acyl groups carry a methyl group in the .alpha. position.

51. A mixture of about 30 mol percent monoethanol amide and about 70 mol percent diethanol amide, the acyl groups of the amides being open chain acyl groups containing from about 11 to about 15 carbon atoms, said mixture being char-acterized in that from about 2 to about 20 mol percent thereof is mono ethanol amide whose acyl groups carry in the a position an alkyl substituent at least two carbon atoms in length.

52. A mixture according to claim 51 wherein the ethanol amides thereof contain 11, 13 and 15 carbon atoms in their acyl groups.

53. A mixture according to claim 52, wherein for each 100 parts by weight thereof, there are from about 25 to about 40 parts of amide with C11 acyl groups, from about 40 to about 50 parts of amide with C13 acyl groups and from about 20 to about 25 parts of amide with C15 acyl groups.

54. A mixture according to Claim 51 further char-acterized in that from about 10 to about 65 mol percent of the mixture is ethanol amide whose acyl groups carry a methyl group in the .alpha. position.

55. A mixture according to Claim 51 further char-acterized in that from about 12 to about 25 mol percent of the mixture is ethanol amide whose acyl groups carry a methyl group in the .alpha. position.

56. A mixture according to Claim 53 further char-acterized in that from about 12 to about 25 mol percent of the mixture is ethanol amide whose acyl groups carry a methyl group in the .alpha. position.

57. A washing composition consisting essentially of (1) the amide composition of Claim 30 and (2) an organic de-tergent surfactant selected from the group consisting of anionic detergents, cationic detergents, nonionic detergents, ampholytic detergents, zwitterionic detergents, and mixtures thereof suitable for use in water, the amount of (1) ranging from about 0.05 to about 25 percent by weight.

58. In a method for washing articles in an aqueous solution of (1) alkanol amide composition and (2) organic detergent surfactant, the improvement which comprises using the composition of Claim 57 as (1) and (2).